KR102209392B1 - Polycarbonate resin composition and optical product including thereof - Google Patents

Abstract

The polycarbonate resin composition according to the present invention relates to a polycarbonate resin composition having excellent thermal stability and optical properties, and an optical molded article including the same, by using a specific additive and two kinds of dyes in combination.

Description

Polycarbonate resin composition and optical molded article comprising the same TECHNICAL FIELD [0002]

The present invention relates to a polycarbonate resin composition excellent in thermal stability and optical properties, and an optical molded article comprising the same.

Polycarbonate is applied to various fields such as exterior materials of electric and electronic products, automobile parts, construction materials, optical parts, etc. due to its excellent impact strength, numerical stability, heat resistance, and transparency.

As the application field of such polycarbonate is expanded in recent years, development of a novel polycarbonate having improved thermal stability and optical properties while maintaining the inherent physical properties of the polycarbonate is required.

In particular, when applied to optical products, it is essential to maintain the desired level of optical properties (excellent shielding rate or transmittance) without deformation of the product even under high temperature conditions, so it is necessary to simultaneously improve thermal stability and optical properties. Technology development is needed.

Accordingly, studies have been attempted to obtain desired physical properties by copolymerizing aromatic diols having different structures to introduce units having different structures into the main chain of polycarbonate or using additional additives. However, most of the technologies have limitations in that the production cost is high, and when chemical resistance or heat resistance is increased, optical properties are conversely deteriorated, and when optical properties are improved, chemical resistance or heat resistance is lowered.

In addition, depending on the applied product group, it is necessary to adjust the transparency of polycarbonate, and for example, when applied to optical products (e.g., lenses), it is necessary to lower the transmittance in a specific wavelength range depending on the purpose of use. there was.

Accordingly, there is still a need for research and development on a novel polycarbonate having excellent heat resistance while satisfying the desired optical properties (excellent shielding rate or transmittance) depending on the application product of the polycarbonate.

The present invention is to provide a polycarbonate resin composition having excellent heat resistance and excellent optical properties by introducing a specific additive and a combination of two dyes.

In addition, the present invention is to provide an optical molded article manufactured from the polycarbonate resin composition having the above.

According to the present invention, a polycarbonate resin having a melt flow rate (MFR, Melt flow rate) of 5 to 15 g/10min according to ASTM D1238; Pentaerythritol tetrastearate; Black dye; And blue dye; including, and having a transmittance of 7% or less at 410 nm according to ASTM D1003, and a yellowing index change value represented by General Formula 1 to be described later is 0.5 or less, providing a polycarbonate resin composition.

Further, according to the present invention, there is provided an optical molded article comprising the polycarbonate resin composition.

Hereinafter, a copolycarbonate according to a specific embodiment of the present invention, a method of manufacturing the same, and a molded article including the same will be described in more detail.

Prior to that, unless expressly stated in the specification, terminology is only intended to refer to specific embodiments and is not intended to limit the invention.

The singular forms used in the present specification also include plural forms unless the phrases clearly indicate the opposite.

The meaning of'comprising' as used herein specifies a specific characteristic, region, integer, step, action, element and/or component, and other specific characteristic, region, integer, step, action, element, component and/or group It does not exclude the existence or addition of

Further, in the present specification, terms including ordinal numbers such as'first' and'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In the case of polycarbonate resin, it is necessary to adjust the transparency of polycarbonate according to the applied product group.For example, when applied to optical products (e.g., lenses), the transmittance in a specific wavelength range is adjusted according to the purpose of use. It was necessary to lower it. However, when an additive is used for the purpose of simply increasing the shielding rate, heat resistance is significantly lowered under high temperature conditions, and there is a problem in that polymer deformation or discoloration occurs during the manufacturing process.

Accordingly, the present inventors realized a low transmittance in a specific wavelength region and a low yellowing index change in a high temperature condition by using a combination of a specific additive and two types of dyes having excellent absorption at a predetermined wavelength. Accordingly, excellent heat resistance and a specific wavelength A polycarbonate resin composition having a high shielding rate in the area was developed.

In the case of manufacturing a product using the polycarbonate resin composition of the present invention described above, the degree of modification or color change of the polymer is remarkably small even under high temperature injection molding conditions during the manufacturing process. In addition, since the product is actually used, it can exhibit excellent physical properties without deformation even in a high temperature environment. In particular, when used as a lens, it can exhibit an excellent shielding rate in a specific visible light region (410 nm), and thus it is preferable because it can be applied to a wide range of general use, industrial use, sports use, and special use.

The polycarbonate resin composition according to an embodiment of the present invention is ASTM D1003 According to the transmittance at 410nm satisfies 7% or less. By simultaneously satisfying the transmittance in the above range and the yellowing index change value described later, all of the above-described physical properties can be satisfied when applied to a product.

When the transmittance at 410 nm is more than 7%, there is a problem that it cannot be applied to various optical molded articles such as general use, industrial use, sports use, and special use. In addition, the transmittance at 410 nm may preferably satisfy 5% or less, more preferably 4.5% or less, and in this case, the desired effect of the present invention may be increased.

The polycarbonate resin composition according to an embodiment of the present invention satisfies a yellowing index change value of 0.5 or less represented by the following general formula 1, and satisfies the yellowing index change value (ΔYI) and transmittance of the above range at the same time. When applied, all of the aforementioned properties can be satisfied:

[General Formula 1]

ΔYI = YI(340℃)-YI(285℃)

YI is a yellowing index value measured according to ASTM D1925 at that temperature.

The parameter of the yellowing index change value (ΔYI) in the above range refers to an index showing excellent heat resistance even in a high-temperature injection process when a product is manufactured using a polycarbonate resin composition, and the temperature change at a high temperature of 285 to 340 is Even if there is, it shows a remarkably low yellowing index change, which means that it exhibits excellent heat resistance not only in the product manufacturing process but also when the product is applied and placed under high temperature environmental conditions.

When the yellowing index change value exceeds 0.5, heat resistance decreases and transmittance decreases, making it unsuitable for use as a lens. In addition, the yellowing index change value may preferably satisfy 0.3 or less, more preferably 0.1 or less, and in this case, the desired effect of the present invention may be increased.

Polycarbonate resin composition according to an embodiment of the present invention is a polycarbonate resin; Pentaerythritol tetrastearate; Black dye; And a blue dye; by including, the above-described specific parameter value is satisfied. Hereinafter, specific characteristics of each component will be described in more detail.

Polycarbonate resin

The term "polycarbonate" used in the present invention refers to a polymer prepared by reacting a diphenol-based compound, phosgene, carbonate ester, or a combination thereof. Polycarbonate resin is very excellent in heat resistance, impact resistance, mechanical strength, transparency, etc., and is widely used in the manufacture of compact discs, transparent sheets, packaging materials, automobile bumpers, UV blocking films, optical lenses, and the like.

Examples of the diphenol-based compound include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also referred to as'bisphenol-A'), 2, 4-bis(4-hydroxyphenyl)-2-methylbutane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro -4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2 ,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl) Ether and the like. Preferably, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane may be used, and in this case, the structure of the polycarbonate resin is as shown in Formula 1:

[Formula 1]

In Formula 1, a is an integer greater than or equal to 1.

The polycarbonate resin may be a mixture of a copolymer prepared from two or more diphenols. In addition, the polycarbonate may be a linear polycarbonate, branched polycarbonate, polyester carbonate copolymer resin, or the like.

Examples of the linear polycarbonate include polycarbonate prepared from bisphenol-A. The branched polycarbonate may include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with diphenols and carbonates. The polyfunctional aromatic compound may be included in an amount of 0.05 mol% to 2 mol% based on the total amount of the branched polycarbonate. Examples of the polyester carbonate copolymer resin include those prepared by reacting a difunctional carboxylic acid with diphenols and carbonates. As the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, and the like may be used.

The polycarbonate resin according to the present invention satisfies a melt flow rate (MFR, Melt flow rate) of 5 to 15 g/10min according to ASTM D1238. When a polycarbonate resin having a melt flow rate in the above range is used, excellent physical properties can be realized when applied to a product by using a combination with the other components described above.

The melt flow rate was measured under a load condition of 1.2 kg at 300° C. according to ASTM D1238.

If the melt flow rate is less than 5 g/min, the processability may decrease, resulting in a problem of lowering productivity, and if the melt flow rate is more than 15 g/min, the resin flow is exceeded under the processing conditions, causing surface defects on the molded product. Can occur. In addition, the melt flow rate may preferably satisfy 6 to 13 g/10 min, more preferably 7 to 10 g/10 min, and in this case, the desired effect of the present invention may be increased.

Preferably, the polycarbonate resin has a weight average molecular weight of 10,000 g/mol to 50,000 g/mol, preferably 25,000 g/mol to 35,000 g/mol. Moldability and workability are excellent in the above range.

Pentaerythritol Tetrastearate ( Pentaerythritol tetrastearate , PETS)

The pentaerythritol tetrastearate component according to the present invention is a component that implements excellent thermal stability and at the same time serves as an auxiliary function to improve shielding properties in a specific wavelength range, and is used in combination with a black dye and a blue dye to be described later to achieve its effect. Can be maximized.

The pentaerythritol tetrastearate may be included in an amount of 0.05 to 5 parts by weight, and preferably 0.1 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. When included in the above content range, excellent heat resistance and shielding property can be implemented, and it is preferable to implement a shielding auxiliary effect in heat resistance and a specific wavelength region. On the other hand, when it is included in an amount of less than 0.05 parts by weight, it is difficult to realize the desired effect in a small amount, and when it is included in an amount of 5 parts by weight, a problem of lowering the mechanical strength may occur.

dyes

The present invention is a component for improving shielding properties in a specific wavelength region by using a combination of a black dye and a blue dye, and is used in combination with the above-described PETS component to realize the effect of improving shielding properties and heat resistance at the same time.

Specifically, the black dye is C.I. It may be a compound of Pigment Black 32 (perylene black), and as a commercially available product, BASF's BK32 (ThermoPlast black x70) may be used.

The black dye can effectively block light in the entire wavelength range, and when used in combination with a PETS component and a blue dye, it is preferable to implement shielding properties suitable for application to a lens.

Said black dye is a polycarbonate resin with respect to 100 parts by weight of 1.0 * ^10-4 to 1.0 * ^10-1 may be included in parts by weight, preferably 1.0 * ^10-4 to 1.0 * ^10-2 parts by weight, more preferably May be included in 1.1*10 ^-3 to 2.0*10 ^-3 parts by weight. When included in the above content range, shielding properties suitable for application to lenses may be implemented. On the other hand, when it is included in an amount less than 1.0*10 ^-4 parts by weight, it is difficult to achieve the desired effect in a small amount, and when included in 1.0*10 ^-1 parts by weight, the transmittance may be excessively decreased.

Specifically, the blue dye may be a compound of Formula 2 below (CAS No. 81-48-1), and as a commercially available product, Lanxess' Blue G (Macrolex Violet B Gran) may be used.

[Formula 2]

.

.

The blue dye may preferably be a reddish blue series.

The blue dye serves to improve the degree of yellowing of the resin, and at the same time, when used in combination with a PETS component and a black dye, heat resistance and shielding properties suitable for application to a lens can be realized. In addition, when a light absorber or the like is additionally used, visible light in the range of 425 to 450 nm can be effectively controlled.

The blue dye may be included in an amount of 1.0 * 10 ^-4 to 1.0 * 10 ^-1 parts by weight, and preferably 1.0 * 10 ^-4 to 1.0 * 10 ^-2 parts by weight, more preferably, based on 100 parts by weight of the polycarbonate resin. May be included in 1.5*10 ^-3 to 2.5*10 ^-3 parts by weight. When included in the above content range, excellent shielding properties can be implemented, and yellowing of the resin can be improved, which is preferable. On the other hand, if it is contained in less than 1.0 * 10 ^-4 parts by weight, it is difficult to realize the desired effect in a small amount, and if it is included in 1.0 * 10 ^-1 parts by weight, it is disadvantageous to commercially apply due to the phenomenon of decrease in YI and transmittance. have.

The polycarbonate resin composition according to the present invention includes the above-described components, and by satisfying specific parameters (transmittance and ΔYI), it is possible to realize heat resistance and excellent optical properties (shielding property at 410 nm), and thus, high temperature during the manufacturing process. Even under injection molding conditions, the degree of alteration or color change of the polymer is remarkably small. In addition, since the product is actually used, it is possible to exhibit excellent physical properties without deformation even in a high temperature environment.

In addition, if necessary, the resin composition is one from the group consisting of antioxidants, heat stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, optical brighteners, ultraviolet absorbers and radiation absorbers commonly used in the art. It may further include additives selected from more than one species.

Optical molded product

In addition, the present invention provides an optical molded article comprising the resin composition. Preferably, the optical molded article is a lens, and is suitable for use in an illumination lens or spectacle lens.

Since the polycarbonate resin composition according to the present invention has excellent heat resistance and shielding properties, it can be usefully used as an optical molded article.

The manufacturing method of the molded article may be manufactured by a method commonly used in the art. For example, it is preferable to mix the above-described polycarbonate resin, pentaerythritol tetrastearate, black dye and blue dye, and additives as necessary, melt-kneading them to produce pellets, and injection-molding the poem into a desired shape.

The melt-kneading is carried out by a method commonly used in the art, such as a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a coneder, a multi-screw extruder, etc. I can. The temperature of the melt-kneading can be appropriately adjusted as necessary.

Next, using the melt-kneaded product or pellets of the resin composition according to the present invention as a raw material, injection molding method, injection compression molding method, extrusion molding method, vacuum molding method, blow molding method, press molding method, pressure molding method, foam molding method, thermal bending molding method, compression Molding methods, such as a molding method, a calendering method, and a rotational molding method, can be applied.

In the case of using the injection molding method, it is placed under a high temperature condition of 200 to 400°C. Since the resin composition according to the present invention has excellent heat resistance, it is preferable because there is little polymer modification or yellowing in the above-described melt-kneading process or injection process.

The size and thickness of the molded product can be appropriately adjusted according to the purpose of use, and the shape of the light guide plate may also have a flat or curved shape depending on the purpose of use.

According to the present invention, a polycarbonate resin composition having excellent heat resistance and excellent optical properties can be provided by introducing a specific additive and two kinds of dyes.

In addition, according to the present invention, it is possible to provide an optical molded article manufactured from a polycarbonate resin composition capable of exhibiting excellent optical properties even under high temperature conditions.

Hereinafter, preferred embodiments are presented to aid in understanding the invention. However, the following examples are for illustrative purposes only, and the invention is not limited thereto.

Example And Comparative example : Preparation of polycarbonate resin composition

Example 1 and 2, Comparative example 1 to 8

A polycarbonate resin composition was prepared by mixing each additive component in the amount shown in Table 1 based on 100 parts by weight of the polycarbonate resin composition.

division
(Ingredient/content)
Parts by weight PC resin additive dyes A B C D E F G Example 1 a-1/
99.404957 b-1/ 0.075 c-1/0.12
c-2/0.12 d-1/
0.05 e-1/
0.35 f-1/0.00014
f-2/0.0002 - Example 2 a-1/
99.404957 b-1/ 0.075 c-1/0.12 d-1/
0.05 e-1/
0.35 f-1/0.00017
f-2/0.0002 - Comparative Example 1 a-1/
99.404957 b-1/ 0.075 c-1/0.12 d-1/
0.05 e-1/
0.35 - g-1/0.00014
g-2/0.0002 Comparative Example 2 a-1/
99.404957 b-1/ 0.075 c-1/0.12 d-1/
0.05 e-1/
0.35 - g-2/0.0002 Comparative Example 3 a-1/
99.404957 b-1/ 0.075 c-1/0.12 d-1/
0.05 e-1/
0.35 - g-3/0.0002 Comparative Example 4 a-1/
99.404957 b-1/ 0.075 c-1/0.12 d-1/
0.05 e-1/
0.35 - g-1/0.00014
g-3/0.0002 Comparative Example 5 a-1/
99.404957 b-1/ 0.075 c-1/0.12 d-1/
0.05 e-2/
0.35 f-1/0.00014
f-2/0.0002 - Comparative Example 6 a-1/
99.404957 b-1/ 0.075 c-1/0.12 d-1/
0.05 e-3/
0.35 f-1/0.00017
f-2/0.0002 - A (PC resin): a-1: Bisphenol A-type linear polycarbonate with Mw 32,000, LG Chem MFR (300, 1.2 kg) of 8 g/10 min
B (antioxidant): b-1 ADEKA PEP36
C (light absorber): c-1: Solvay's UV3638,--- c-2: Clariant's B-Cap
D (chain extension): d-1: BASF ADR4370F(4468)
E (additive): e-1: pentaerythritol tetrastearate/ e-2: GMS (Glycerol mono stearate)/ e-3: GTS (Glycerol Tri stearate)
F (dye): f-1 (blue, Reddish Blue): Lanxess Blue G/ f-2 (black): BASF BK32
G (dye): g-1 (blue): Lanxess BL12 (CAS No. 61969-44-6), g-2 (red): Lanxess RP04 (CAS No. 6829-22-7), g-3 (Greenish Blue): Lanxess Violet 3R

Experimental example

Pellet samples were prepared at a rate of 55 kg per hour in a twin-screw extruder (L/D=36, Φ=45, barrel temperature 240°C) from the resin composition prepared according to the prepared Examples and Comparative Examples, and For, the properties were measured by the following method.

(1) Melt flow rate (MFR, Melt flow rate, g/min)

According to ASTM D1238, using the Toyoseiki Melt Indexer G-02 equipment, the melt flow rate was measured at 300°C under a 1.2kg load condition, and the results are shown in Table 2 below.

(2) transmittance (%)

According to ASTM D1003, using Hunter Lab equipment, the transmittance at 410 nm was measured under transmission conditions of 350 to 1050 nm, and the results are shown in Table 2 below.

(3) Yellowing index change value (ΔYI)

According to ASTM D1925, using the Hunter Lab equipment, the yellowing index was measured under transmission conditions of 350 to 1050 nm. The yellowing index was measured at 285°C and 340°C while raising the temperature from 285°C to 340°C for 20 minutes, and the yellowing index change value according to the following general formula 1 was calculated, and the results are shown in Table 2 below.

[General Formula 1]

ΔYI = YI(340℃)-YI(285℃)

division 410nm transmittance (%) ΔYI Example 1 4.4 0.23 Example 2 4.6 0.25 Comparative Example 1 8.7 0.25 Comparative Example 2 7.8 0.26 Comparative Example 3 8.4 0.25 Comparative Example 4 7.2 0.26 Comparative Example 5 4.5 2.46 Comparative Example 6 5.2 2.67

As can be seen in Table 2, it was confirmed that heat resistance and excellent optical properties can be simultaneously implemented by introducing a specific additive and two kinds of dyes in the case of the embodiments according to the present invention.

In the case of comparative examples that deviate from the combination components limited by the present invention, it was confirmed that the heat resistance under high temperature conditions was lowered, so that the yellowing degree change value was significantly increased, or the transmittance was increased at 410 nm, so that it was unsuitable for use in optical molded articles, especially lenses .

Claims (9)

Polycarbonate resin with a melt flow rate (MFR) of 5 to 15 g/10min according to ASTM D1238; Pentaerythritol tetrastearate; Black dye; And a blue dye; Including,
With respect to the polycarbonate resin of 100 parts by weight of pentaerythritol tetra-stearate, 0.05 to 5 parts by weight of a black dye 1.0 * ^10-4 to 1.0 * ^10-1 parts by weight of a blue dye 1.0 * ^10-4 to 1.0 * ¹⁰ Including ^{1 part by} weight,
The transmittance at 410nm according to ASTM D1003 is 7% or less,
A polycarbonate resin composition having a yellowing index change value (ΔYI) of 0.5 or less represented by the following General Formula 1:
[General Formula 1]
ΔYI = YI(340℃)-YI(285℃)
YI is a yellowing index value measured according to ASTM D1925 at that temperature.
The method of claim 1,
The polycarbonate resin comprises a repeating unit represented by the following formula (1), a polycarbonate resin composition:
[Formula 1]

In Formula 1, a is an integer greater than or equal to 1.
The method of claim 1,
The polycarbonate resin has a weight average molecular weight of 10,000 g/mol to 50,000 g/mol, a polycarbonate resin composition.
The method of claim 1,
The black dye is CI pigment black 32, a polycarbonate resin composition.
The method of claim 1,
The blue dye is a compound represented by the following formula (2), a polycarbonate resin composition:
[Formula 2]

.
delete The method of claim 1,
The polycarbonate resin composition further comprises one or more additives selected from the group consisting of antioxidants, heat stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, ultraviolet absorbers and optical brighteners. Composition.
An optical molded article comprising the polycarbonate resin composition of any one of claims 1 to 5 and 7.
The method of claim 8,
The optical molded article, characterized in that the optical molded article is a lens.